Preprogrammed assembly of supramolecular polymer networks via the controlled disassembly of a metastable rotaxane

Abstract

In our daily life, some of the most valuable commodities are preprogrammed or preassembled by a manufacturer; the end-user puts together the final product and gathers properties or function as desired. Here, we present a chemical approach to preassembled materials, namely supramolecular polymer networks (SPNs), which wait for an operator’s command to organize autonomously. In this prototypical system, the controlled disassembly of a metastable interlocked molecule (rotaxane) liberates an active species to the medium. This species crosslinks a ring-containing polymer and assembles with a reporting macrocycle to produce colorful SPNs. We demonstrate that by using identical preprogrammed systems, one can access multiple supramolecular polymer networks with different degrees of fluidity (μ* = 2.5 to 624 Pa s-1) and color, all as desired by the end-user.

The Role of Dethreading Process in Pseudorotaxanes and Rotaxanes towards Advanced Applications: Recent Examples

“…Mechanically interlocked molecules (MIMs) are a type of compounds constituted by components which are bonded together through noncovalent interactions, forming a mechanical bond [1–3] . Within the range of intertwined compounds, rotaxanes are postulated as ideal candidates for the design of molecular machines, developing applications in a wide range of fields, [4–6] such as catalysis, [7–14] materials science [15–24] or medicinal chemistry [25–27] …”

“…Mechanically interlocked molecules (MIMs) are a type of compounds constituted by components which are bonded together through noncovalent interactions, forming a mechanical bond. [1][2][3] Within the range of intertwined compounds, rotaxanes are postulated as ideal candidates for the design of molecular machines, developing applications in a wide range of fields, [4][5][6] such as catalysis, [7][8][9][10][11][12][13][14] materials science [15][16][17][18][19][20][21][22][23][24] or medicinal chemistry. [25][26][27] Usually, the design of these structures seeks the stability of the mechanical bond, thus preventing the dissociation of the different components in order to carry out a specific function.…”

Control of the assembly of a cyclic hetero[4]pseudorotaxane from a self-complementary [2]rotaxane

“…In this line, compounds able to self-assemble and form supramolecular species or polymers through the formation of mechanical bonds are considered a breakthrough. 7 Supramolecular chemistry provides powerful tools for the precise construction of these inspiring architectures, assembled through the establishment of intermolecular non-covalent interactions. 8 In the most useful examples of these supramolecular architectures, changes in some key parameters (solvent polarity, concentration, temperature, …) allow to control its level of organization, as monomers ([1]rotaxanes) 9 dimers (lineal or [ c 2]daisy chains), 10 trimers 11 or oligomers with more complex skeletons.…”

Balancing ring and stopper group size to control the stability of doubly threaded [3]rotaxanes

“…[23][24][25][26] Accessing different slippage rates in these metastable rotaxanes is possible and such interlocked compounds have been shown to be useful as a means of chemical protection, 27,28 constructing molecular pumps, [29][30][31] and the assembly of more complex architectures such as molecular containers 32 and supramolecular networks. 33 An important design parameter that has emerged in rotaxane synthesis and application is macrocycle size. [34][35][36][37][38][39][40][41][42][43] Specifically, control over the size of the ring(s) employed in rotaxane structures has allowed researchers to influence their ring mobility, 35 impact their electrochemical properties, 38 access molecular shuttles, 39 develop means of programmable chemical protection 40 and more.…”

“…23–26 Accessing different slippage rates in these metastable rotaxanes is possible and such interlocked compounds have been shown to be useful as a means of chemical protection, 27,28 constructing molecular pumps, 29–31 and the assembly of more complex architectures such as molecular containers 32 and supramolecular networks. 33…”